Secondary ethers of polyhydric



Reiuued July 13, 1943 Theodore W. Evans, Berkeley, and Edwin F.

Bullard, Oakland. Calif" asslgnors to Shell Development Company, San Francisco, Call!., a corporation of Delaware No Drawing. Original No. 2,197,467, dated April 16, 1940, Serial No. 190.028, February 11, 1938, which is a division of Serial No. 115,638, December 12, 1938. Application for reissue November 29, 1940, Serial No. 387,794

8 Claims.

This invention relates to new chemical compounds and more particularly to new aliphatic trlhydric alcohol ethers characterized by the substitution of an alkoxy group 01 an aliphatic secondary alcohol for at least one of the hydroxy groups of the trihydric alcohol.

An object of the invention is to provide a novel class of secondary ethers of trihydric alcohols which have value for a great many technica1 uses and are also valuable as intermediates in the preparation or useful trihydric alcohols and other derivatives thereof. A further object of the invention lies in the preparation of new intermediates from which the herein disclosed ethers may be readily prepared.

Secondary ethers of polyhydric alcohols of the class consisting of aliphatic trihydric alcohols, one hydroxy group of which has been substituted by the alkoxy group of an aliphatic secondary alcohol; alcohol trlhydric alcohols, two hydroxy groups of which have been substituted by the alkoxy groups of aliphatic secondary alcohols, at least one of said alkoxy groups containing'at least four carbon atoms; and aliphatic trihydric alcohols, each hydroxy group of which has been substituted by the alkoxy group of an aliphatic secondary alcohol, have been prepared and described for the first time.

The invention is described with particular reierence to the secondary ether of the glycerols, the term "glycerol" embracing, in addition to glycerol, its homologues, analogues and trihydric substitution products. Secondary mono-ethers o1 glycerols, which are embraced within the scope of the invention, include, among others, the follow,- ing: alpha isopropyl ether of glycerol, beta isopropyl ether of glycerol, alpha secondary butyl ether of glycerol, beta secondary butyl ether of glycerol, alpha secondary amyl ether of glycerol, beta secondary amyl ether of glycerol, the secondary hexyl ethers of glycerol, the secondary heptyl ethers of glycerol and the like and their homologues, analogues and suitable substitution products: alpha isopropyl ether of beta-methyl glycerol, beta isopropyl ether of beta-methyl glycerol, alpha secondary butyl ether of beta-methyl glycerol, beta secondary butyl ether 01 betamethyl glycerol, alpha secondary amyl ether of beta-methyl glycerol, the secondary hexyl ethers of beta-methyl glycerol, the secondary heptyl ethers of beta-methyl glycerol and the like and their homologues, analogues and suitable substitution products the isopropyl, secondary butyl, secondary amyl, secondary hexyl, secondary hepbeta-propyl-, beta-hexyland the like'glycerols; the isopropyl, secondary butyl, secondary amyl, secondary hexyl, secondaryheptyl and the like monoethers of the alpha-methyl, alpha-ethylalpha-propyl and the like glycerols; as well as, the secondary monoethers ot the alpha alpha substituted glycerols as alpha methyl, alpha'- ethyl glycerol, alpha beta substituted glycerols as alpha methyl, beta-methyl glycerol and the like.

It is seen that, in the above described novel compounds, one hydroxy group 01 the trihydric alcohol has been replaced by the alkoxy group of an aliphatic secondary alcohol as isopropyl alcohol, secondary butyl alcohol, secondary amyl alcohol, etc. One or both of the other hydroxy groups may be substituted by the alkoxy, aralkoxy or aryloxy groups of primary or tertiary alcohols or of phenolic compounds, or by the negative radicals of aliphatic carboirylic acids, such as in alpha-methyl, alpha secondary butyl diether of glycerol, allyl, secondary butyl diether of glycerol and phenyl, secondary butyl diether of glycerol. 4

Disecondary diethers of glycerols, which are within the scope of the invention, include, among others, the following: alpha isopropyl, alpha secondary butyl diether 01 glycerol, alpha beta diisopropyl diether of glycerol, alpha, alpha disecondary butyl diether of glycerol, alpha isopropyl, alpha secondary amyl diether 01' glycerol, alpha secondary butyl, alpha secondary amyl diether of glycerol, alpha, alpha disecondary amyl diether of glycerol, alpha isopropyl, alpha secondary hexyl diether of glycerol, alpha secondary butyl, alpha secondary hexyl diether of glycerol, alpha secondary butyl, beta secondary butyl diether of glycerol, alpha secondary butyl, beta isopropyl diether of glycerol, alpha, alpha diisopropyl diether of beta-methyl glycerol, alpha, alpha disecondary butyl diether of beta-methyl glycerol, alpha, beta diisopropyl diether of betamethyl glycerol, the symmetrical and mixed disecondary diethers oi the beta-ethyl-, betapropyl-beta-butyl and the like glycerols, the symmetrical and mixed disecondary diethers 01' the alpha substituted glycerols, and the like and their homologues, analogues and suitable substitution products. The remaining hydroxy group of the above-listed disecondary diethers or glycerols may be substituted by the alkoxy, aralkoxy or aryloxy group of a primary or tertiary alcohol or of a phenolic compound, or it may be s bstituted by the negative radical 01 an organic carboiwlic acid.

tyl and the like monoethers or the beta-ethyl-. I! Trisecondary triethers of s ycerols, which are within the scope of the invention, include, among others, the following: trilsomopyl triether of glycerol, trisecondary butyl triether of glycerol, trisecondary amyl triether of glycerol, trisecondary hexyl triether of glycerol, alpha, alpha diisopropyl, beta secondary butyl triether of glycerol, alpha, beta diisopropyl, alpha secondary butyl triether or glycerol alpha, alpha diiso- 5 propyl beta secondary amyl triether of glycerol, alpha, alpha disecondary butyl, beta isopropyl triether of glycerol, and the like trisecondary triethersof the glycerols as beta-methyl glycerol, beta-ethyl glycerol, beta-propyl glycerol, alphamethyl glycerol, alpha, alpha dimethyl glycerol, etc., wherein the hydroxy groups are substituted by the same or different alkyl radicals of allphatic secondary alcohols.

A particularly useful and readily prepared group of secondary ethers of polyhydric alcohols comprises the secondary monoethers, the disecondary diethers wherein one of the secondary alcohol radicals contains at least four carbon atoms, and the trisecondary triethers of glycerol.

The secondary monoethers of glycerol may be represented by the formulae:

and HOCHa-CHOR-CHsOH, wherein R represents the alhl radical of an aliphatic secondary alcohol.

The disecondary diethers of glycerol with which we are principally concerned may be represented by the formulae:

a-o-cm cnon-cm-o a', Ho-cm-cHoa-cmon' wherein R, R, and B" may be the same or different and represent alkyl radicals of aliphatic secondary alcohols.

In our U. 8. Patent No. 2,067,385, which issued January 12, 1937, with which the parent application of which this application is a division was copending and a continuation-in-part thereof, we have described and claimed a process for the preparation of secondary polyhydric alcohol ethers, which process comprises reacting a secondary-base olefine, as propylene, secondary butylene, secondary amylene, etc., with an allphatic polyhydric alcohol in the presence of a condensing agent, preferably an acid-acting condensing agent, which promotes a condensing action between the oleflne and the alcohol. This process is suitable for the production of some 01' the secondary ethers of trihydric alcohols herein described. We have, in addition, discovered that there are other methods of preparing such secondary ethers of trihydric alcohols.

One of such other methods comprises reacting a halohydrin of the trihydric alcohol to be etherifled with an alkali metal salt of the desired aliphatic secondary alcohol. For example, it it is desired to prepare the alpha isopropyl ether of glycerol, dichlorhydrin may be reacted with the isopropyl alcoholate or sodium to yield the isopropyl ether or glycidol which can be readily hydrated to the desired alpha isopropyl monoether of glycerol. This manner oi preparing the secondary ethers oi trihydric alcohols is described "in detail in the illustrative examples.

The invention is illustrated but not limited by the following examples which describe the preparation of representative secondary ethers of trihydric alcohols. The parts are by weight.

Example I About 54.5 parts of sodium were dissolved in about 1000 parts of secondary butyl alcohol. This solution was stirred and heated at about 70 C., while about 150 parts or dichlorhydrin were added. when all of the dichlorhydrin had been added, the stirring was continued and the mixture heated at about C. for about 1.5 hours. At the end oi this time, the mixture was cooled. filtered to separate sodium chloride. and distilled under a subatmospherlc pressure. Two reaction products were isolated.

The lower boiling product (B. P. 52' C. at 14 mm. of mercury) was the secondary butyl ether or glycidol oi the formula I o CrHs-CH-O-CHr-fil- K1 in This novel compound has a speciiic gravity This compound boils at a temperature 0! C. under a pressureof 14 mm. of mercury, and it has a specific gravity v of 0.9125. This ether is a solvent for nitrocellulose. It is only slightly soluble in water.

Example If About 51 parts of sodium were dissolved in about 750 parts of secondary amyl alcohol. This solution was stirred and maintained at room temperature while about parts of dichlorhydrin were added slowly over a period of about one hour. After all of the dichlorhydrin had been added, the temperature of the mixture was raised to about'90 C. and the stirring continued for about one hour. At the end of this time, the cooled mixture was distilled under a subatmospheric pressure to separate the reaction product irom'the precipitated salt. The first distillate was then redistilled under a subatmospheric pressure to recover the pure product. The product was the secondary amyl ether of glycidol of the formula 0 Can-ca-o-cm-(n- HI This novel compound has a boiling temperature of 74 C. under a pressure of 16 mm. of mercury. Its specific gravity is 0.9056. The glycidol ether possesses a limited water solubility and it is a good solvent for nitrocellulose.

The secondary amyl ether of glycidol was hydrated to the corresponding alpha secondary amyl ether of glycerol by the following method: About 40 parts of the glycidol ether, 400 parts of water and 0.15 part of sulphuric acid were mixed and the mixture stirred and heated under reflux for about five hours. At the end of this time the reaction mixtur was neutralized and distilled under a subatmospheric pressure. The alpha secondary amyl ether of glycerol was obtained in good yield. This compound boils at 102 C. under a pressure of 3 mm. and it has a specific gravity The novel secondary ethers of trihydric alcohols are for the most part colorless, more or less viscous liquids of high boiling temperature and negligible vapor pressure at room temperature. The secondary ethers, particularly the secondary monoethers, may be used as substitutes for glycerol in a great many processes. In numerous cases they are more advantageously used than the glycerols because of their lower hydroscopicity and greater solvent power for certain materials. For example, the secondary ethers of trihydric alcohols comprehended by the invention are useful as ingredients of textile treatment media, as reagents in the manufacture of explosives, as perfume flxatives, as constituents of lubricating compositions, as constituents of anti-freeze mixtures for use in the cooling systems of internal combustion engines, as heat-transferring media in indirect heat conduction systems, as reactants in the preparation of resins, etc.

The novel trihydric alcohol ethers are particularly useful as solvents. Many of them are good nitrocellulose solvents and are useful as plasticizers for cellulose ethers and esters. They may be used as such or admixed with other substances, as extracting agents for organic substances as alkaloids, essential oils, essences and the like. They are excellent solvents for acetylene, and they may be used as scrubbing agents to recover acetylene from gaseous mixtures. The glycerol ethers, particularly those of lower molecular weight, are excellent solvents for acidic gases, particularly hydrocyanic acid. Further, the secondary ethers of trihydric alcohols are useful intermediates in the preparation of trihydric alcohols and trihydric alcohol derivatives.

This application is a division of our copending application, Serial No. 115,636, filed December 12, 1936, which was copending with application. Serial No. 722,567, filed April 28, 1934, which issued as U. 8. Patent 2,067,385 on January 12, 1937.

substituted by the alkoxy groups of aliphatic secondary alcohols containing at least six carbon atoms.

3. The glycerol disecondary diether of the general formula 3 (C:H|0I)/ wherein R represents the alkyl radical of an allphatic secondary alcohol, and R1 represents the alkyl radical of an aliphatic secondary alcohol containing at least six carbon atoms to the molecule.

4. The glycerol disecondary diether of the general formula wherein R and R1 are the alkyl radicals of aliphatic secondary alcohols at least one of which contains at least six carbon atoms.

5. The glycerol disecondary diether of the general formula wherein R and R1 are the alkyl radicals of allphatic secondary alcohols at least one of which contains at least six carbon atoms.

6. The glycerol disecondary diether of the general formula CIHr-CHO-CHrCHOH-CH1OR wherein R1 represents the alkyl radical of an allphatic secondary alcohol containing at least six carbon atoms.

7. The glycerol disecondary diether of the general formula ClHr-CH0CHr-CEORiCHl0H wherein R1 represents the alkyl radical of an allphatic secondary alcohol containing at least six carbon atoms.

8. The glycerol disecondary diether of the general formula wherein R1 represents the alkyl radical of an aliphatic secondary alcohol containing at least six carbon atoms.

THEODORE w. EVANS. EDWIN r. numisan. 

